US4253929A - Method for denitration of tobacco employing electrodialysis - Google Patents

Method for denitration of tobacco employing electrodialysis Download PDF

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US4253929A
US4253929A US06/127,479 US12747980A US4253929A US 4253929 A US4253929 A US 4253929A US 12747980 A US12747980 A US 12747980A US 4253929 A US4253929 A US 4253929A
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tobacco
extract
electrodialysis
membranes
membrane
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Gus D. Keritsis
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Philip Morris USA Inc
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Philip Morris USA Inc
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Priority to US06/127,479 priority Critical patent/US4253929A/en
Priority to DE8080105313T priority patent/DE3069870D1/de
Priority to CA359,584A priority patent/CA1132943A/en
Priority to EP80105313A priority patent/EP0035052B1/en
Priority to US06/216,803 priority patent/US4302308A/en
Priority to GR64167A priority patent/GR73893B/el
Priority to BR8101234A priority patent/BR8101234A/pt
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Publication of US4253929A publication Critical patent/US4253929A/en
Priority to JP3109281A priority patent/JPS56140880A/ja
Priority to DK97481A priority patent/DK97481A/da
Priority to PH25314A priority patent/PH16773A/en
Priority to ES500050A priority patent/ES8205347A1/es
Priority to AU68080/81A priority patent/AU540522B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/24—Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts

Definitions

  • This invention relates to a method for denitrating tobacco to effect a reduction in delivery of nitrogen oxides in tobacco smoke, wherein the tobacco is denitrated via electrodialysis.
  • Tobacco contains a number of nitrogen containing substances which during the burning of the tobacco yield various components in the smoke. Removal of some of these smoke components, such as the oxides of nitrogen, is considered desirable.
  • Nitrate salts such as potassium, calcium and magnesium nitrates
  • Nitrate salts are a major class of nitrogenous substances which are precursors for nitrogen oxides, especially nitric oxide. These nitrate salts are normally found in great abundance in burley tobacco stems and strip and to a lesser degree in flue-cured tobacco stems and in reconstituted tobaccos which utilize these components. Attempts have been made to reduce or remove the nitrate from these tobaccos to bring about a significant reduction in the oxides of nitrogen delivered in their smoke. Among the techniques which have been employed to this end are extraction methods whereby the nitrates are removed from the tobacco material.
  • tobacco materials are generally contacted with water.
  • an extract containing the tobacco solubles including the nitrate salts is formed.
  • the extract is collected and may be discarded or may be treated to remove the nitrate ions.
  • the denitrated extract may thereupon be reapplied to the fibrous insoluble tobacco material from which it was originally removed.
  • U.S. Pat. Nos. 4,131,118 and 4,131,117 describe denitration of an aqueous tobacco extract by crystallizing the nitrate as potassium nitrate followed by reapplication of the denitrated extract to the tobacco.
  • denitration of tobacco extracts is effected by means of ion-retardation resins which retard ionic material, specifically potassium nitrate, while non-ionic constituents in the tobacco extracts pass unaffected. In the practice of this method rapid neutralization of the resins results, necessitating plant shutdown for regeneration employing costly chemical treatments.
  • U.S. Pat. No. 3,616,801 describes a process for improving the tobacco burn properties, smoke flavor and ash by controlling the ion content of the tobacco.
  • the proportion of metallic ions in an aqueous tobacco extract is adjusted, followed by reapplication of the treated extract to the tobacco.
  • the treaments suggested for adjusting the metal ion content are ion exchange and membrane electrodialysis. Removal of potassium ions and their replacement with ammonium, hydrogen, calcium or magnesium ions are particularly desirable in the practice of this process. Other ions, including nitrate, may also be removed to improve the tobacco properties.
  • substantial quantities of various tobacco solubles, including both nitrate and potassium ions were removed by means of electrodialysis.
  • the present invention provides a method for maximizing the removal of nitrates from tobacco extracts, while minimizing the removal of other desirable tobacco solubles.
  • an aqueous tobacco extract having a solids content of about 5-50% and a resistivity of about 8-50 ohm-cm is rapidly circulated through the alternate cells of an electrodialysis unit which comprise an anion permeable membrane toward the anode spaced no more than about 0.04 inches from an anion impermeable membrane toward the cathode while circulating brine in the remaining cells and applying about 0.5 to about 2.0 volts/cell pair, thereby selectively extracting the nitrate salts into the brine cells, without substantial removal of other tobacco solubles.
  • the thus treated extract may then be applied to fibrous tobacco materials from which the tobacco solubles have been extracted.
  • Smoking tobacco products containing tobacco which has been treated in this manner deliver substantially reduced levels of nitric oxide during combustion.
  • FIG. 1 is a schematic diagram of an electrodialysis stack for selectively removing nitrate salts from tobacco extracts.
  • FIG. 2 is a schematic diagram of a membrane electrodialysis stack employing electro-regenerated ion exchange resins.
  • FIG. 3 is a schematic diagram of the mechanism of a cell in an electrodialysis stack employing electro-regenerated ion exchange resins.
  • denitration of tobacco extracts is effected by means of membrane electro-dialysis.
  • substantial removal of nitrate salts from tobacco material may be effected, with minimal removal of other solubles present in the tobacco material.
  • substantial reduction in nitrogen oxide delivery by tobacco smoke is achieved efficiently in a commercially feasible manner with minimal effects on other characteristics of the tobacco material.
  • an aqueous tobacco extract which contains 5-50% solids content, and a resistivity of 8-50 ohm-cm, is formed.
  • An extract containing 10-30% solids and having a resistivity of 10-30 ohm-cm is preferred.
  • an extract may be produced by contacting a tobacco material with an aqueous solution in order to extract the soluble components, including nitrate salts.
  • the aqueous solution employed may be water or preferably a denitrated aqueous extract of tobacco containing tobacco solubles.
  • the extraction can be effected using 5:1 to 100:1 aqueous solution to tobacco ratio (w/w) at 20°-100° C., preferably 60°-95° C., generally for a period of time ranging from a few seconds to several minutes depending on the particular temperature and volume of water or soluble used, although longer periods may be employed.
  • the aqueous tobacco extract is separated from the insoluble fibrous tobacco residue, employing conventional solid-liquid separation techniques. For example, pressing, centrifugation and filtration techniques may be employed.
  • pressing, centrifugation and filtration techniques may be employed.
  • the wetted tobacco is pressed or centrifuged, at the end of the extraction time to remove the excess water and residual nitrate salts that may be present on the tobacco surface and in suspension.
  • the separated tobacco extract is treated to achieve the desired solids content and resistivity.
  • the extract is subjected to electrodialysis employing conditions such that maximum removal of nitrate salts with minimal removal of desirable tobacco solubles is effected in a commercially practical manner.
  • electrodialysis in accordance with the present invention entails rapid circulation of the extract through electrodialysis cells comprising closely spaced anion permeable and anion impermeable membranes while applying a low voltage.
  • the extract is recombined with the insoluble tobacco material from which it was removed.
  • potassium ions as well as nitrate ions
  • potassium salts may be added directly to the extracted tobacco.
  • the potassium salts suitable for this purpose are potassium phosphate, acetate, citrate, malate and carbonate.
  • the extract Prior to reapplication the extract may be concentrated if necessary or desired. This may be accomplished by evaporation methods, such as thin film flash evaporation, reverse osmosis or ultra-microfiltration, as well as other conventional concentration techniques.
  • the reapplication may be effected by any suitable means such as spraying, coating, dipping or slurry processes.
  • the tobacco may be dried or otherwise processed to put it in condition for use in tobacco products. Thereupon treated tobacco may be used in any smoking tobacco product desired. Any such smoking tobacco product will exhibit reduced delivery of nitrogen oxides during combustion.
  • the membranes are arranged in stacks which are disposed between an anode and a cathode.
  • the nitrate ions in the extract can be removed either as potassium nitrate or selectively as NO 3 - , leaving the potassium ions substantially intact.
  • the stacks which may be employed in the practice of the present invention comprise anion permeable or neutral membranes alternating with cation permeable or bipolar membranes to form alternate brine and extract cells.
  • the permeable membranes alternately concentrate and dilute the ionic species (particularly K + and NO 3 - ) in the tobacco extract in contact with them.
  • the membranes are separated by spacers which are designed and manifolded to provide uniform flow distribution of tobacco extract.
  • the tobacco extract flows through those alternate cells which have an anionic or neutral membrane (A) toward the anode and a cationic (C) or bipolar membrane toward the cathode, while the extracting medium or brine flows through the remaining cells.
  • the brine is thus confined between an anion impermeable membrane toward the anode and an anion permeable membrane toward the cathode.
  • the anions present in the tobacco extract cells migrate toward the anode upon imposition of an electric potential. Since the brine cells into which the nitrate ions migrate have an anion impermeable membrane toward the anode, the nitrate ions remain and are concentrated in the brine cells and can thus be removed from the system. Potassium ions may migrate in a similar manner toward the cathode upon imposition of an electrical potential if a cation permeable membrane is employed. On the other hand, the potassium ions will be retained in the tobacco extract when a potential is applied if an impermeable bipolar type membrane is employed.
  • FIG. 1 is a schematic diagram of an electrodialysis stack in vessel V which may be utilized in the practice of the present invention and in which a cation permeable membrane and K 2 SO 4 electrolyte are employed.
  • the electrodes employed in the electrodialysis unit may be carbon, stainless steel, platinum, or other type of non-corrosive conductive material that does not react with the electrolyte and does not introduce metallic ions in solution, especially polyvalent ions such as Cu ++ and Al +++ , that may react with the ionic membrane or with the tobacco solubles and cause membrane fouling and/or scaling on the membrane surface.
  • a hastelloy carbon cathode plates and platinized columbium anode plates are employed.
  • the solutions in the electrode cells may be different for the anode and the cathode, but preferably are the same.
  • These electrolyte solutions should comprise an approximately 0.1 N solution of an alkali metal salt, preferably a potassium salt of an anion that will not react and will create minimum gas at the electrodes or of an anion that will not foul the membranes nor precipitate polyvalent cations such as Ca ++ , Mg ++ , Al +++ , and the like on the surface of the membrane.
  • an alkali metal salt preferably a potassium salt of an anion that will not react and will create minimum gas at the electrodes or of an anion that will not foul the membranes nor precipitate polyvalent cations such as Ca ++ , Mg ++ , Al +++ , and the like on the surface of the membrane.
  • electrolytes that are particularly preferred are those containing potassium acetate or sulfate and having a pH of about 2-5 by adding H 2 SO 4 , acetic acid or the like.
  • the purpose of the electrolyte solution is three-fold, namely to increase and maintain the conductivity of the solution, to cool the electrodes and make them more efficient conductors, and to remove the hydrogen bubbles that accumulate on the electrode surfaces.
  • the electrolyte is continuously recirculated to an electrolyte container which is vented to allow hydrogen gas to escape thereby preventing the gas from being recirculated to the electrodes.
  • a non-ionic wetting agent such as glycerine, Triton X-100 or the like may be employed.
  • circulation of the electrolyte at a rapid rate will facilitate removal of oxygen or hydrogen gas bubbles from the electrodes.
  • the membranes employed to isolate the electrodes may be of the same nature and thickness as those used in the overall stack. However, these membranes are preferably thicker, more ionic and tighter (less porous). Also, the spacers that are placed between the electrodes and the anode-cathode membranes may be of the same thickness as those used in the overall stack, but preferably they should be thicker, i.e., about twice the thickness of the remaining spacers to allow a greater circulation ratio of electrolyte on the surface of the electrodes.
  • the brine solution will typically be aqueous. It is preferable that a small concentration of ionic material be present in the brine during the initial phase of operation in order to create some conductivity.
  • the brine may initially be seeded to 0.1 weight percent potassium or sodium nitrate, chloride or acetate, or nitric, hydrochloric, or acetic acid or with potassium or sodium hydroxide.
  • the initial seeding of the brine to about 0.1 weight percent should be made with ions that are water soluble and will not affect the membranes.
  • the brine may be recirculated through the system until the extraction of nitrate ions thereby is no longer efficiently effected.
  • the anion permeable membranes may be neutral or ionic membranes having a positive fixed electrical charge. Positively charged membranes which will attract and pass anions and repel cations and are thus anion permeable. Cation permeable membranes are negatively charged and will attract and pass cations and repel anions. Neutral membranes will allow either anions or cations to pass through when a voltage is applied across the ionic solution that is confined between such membranes.
  • Bipolar type membranes are cation and anion impermeable membranes which contain positively charged groups on one face and negatively charged groups on the other. When these membranes are placed such that the membrane surface which contains the negatively charged groups is toward the cathode and the positively charged surface is facing the anode, the anions which are attracted towards the anode are repelled by the negatively charged membrane surface and the cations which are attracted toward the cathode are repelled and neither ion is allowed to pass through. Bipolar type characteristics can be achieved with a single membrane or two membranes, one anionic and one cationic, can be placed directly against each other to simulate a bipolar membrane.
  • membranes should be employed which not only have the appropriate cation or anion selectivity, but which also have a tightness sufficient to minimize transfer of nonelectrolyte substances.
  • Membrane tightness is a term used to describe membranes according to the amounts of nonelectrolyte substances that are transferred or accompany the ionic transfer during electrodialysis. This parameter is controlled during membrane manufacture by adjusting average pore sizes or total pore volumes. The effect of pore size in chemical separations of various substances on the basis of molecular weight is well developed and described in microfiltration, ultrafiltration or reverse osmosis technologies.
  • Membranes that contain about ⁇ 25% water are considered to be very tight membranes, whereas those membranes that contain about ⁇ 50% water are considered to be very loose membranes.
  • Membranes containing intermediate amounts of water are of intermediate degrees of tightness. Those membranes which contain the higher amount of water will allow a greater amount of soluble substances of a given molecular weight to intrude in the membrane matrix, and to reach equilibrium and with such membranes a greater amount of water is transferred with the ionic species into the concentrating stream (brine compartment) when an electrical potential is applied. A greater quantity of nonionic (nonelectrolyte) substances is transferred into the brine or concentrating stream.
  • Such a membrane is classified as loose while a membrane having the same porosity characteristics but containing a lesser amount of water is considered to be a tighter membrane, since a smaller amount of nonelectrolyte substances will dissolve in the water in the membrane matrix of the latter membrane and because a lower amount of water is transferred with the ionic species.
  • tight membranes having small pore sizes or volumes and/or low water contents are most effective in minimizing transfer of nonionic tobacco solubles into the brine cells.
  • the number and dimensions of the cells will depend upon the desired treatment rates, the size of commercially available membranes, the viscosity of the aqueous tobacco solubles and the need to maintain an acceptable flow rate at a pumping pressure below the rupturing point of the membranes. Other factors that determine the number and dimension of cells are the operating voltage, the amount of nitrate in the aqueous tobacco solubles, the solubles temperature, the desired degree of denitration, the resistivity of the membranes and the distance or thickness of the cells, and the desired mode of operation, viz. continuous vs. batch. Generally for a given system (voltage, nitrate level, treatment rate) with thinner, more ionic and smaller spacing between cell membranes, smaller membrane area or fewer cells will be required.
  • the concentration of the tobacco extract is generally limited on the one hand by flow rate, which depends on the presence of substances that increse the extract's viscosity, and, on the other hand, by efficient denitration, which depends on the concentration of nitrate ions. Concentrations should be kept low enough to avoid membrane deposits and to permit flow without excessive resistance. As a practical manner, viscosity is the upper limit for tobacco extract concentration. At the low end of the range, the power required relative to the degree of deionization becomes the limiting factor. It has been found that tobacco extracts having between 5-50% solids and a resistivity of 8-50 ohm-cm, are suitable for use in the present process. Preferably, extracts having 10-30% solids and a resistivity of 10-30 ohm-cm are treated in accordance with the invention.
  • the degree to which a solution is demineralized is proportional to the electrical current flowing through the stack.
  • the current is limited by the electrical resistance of the stack components and the maximum voltage which can be applied before overheating occurs. Therefore, in solutions requiring a large amount of salt transfer, it becomes necessary to pass the solution through the stack a number of times (batch operation) or through several stacks in series (continuous) until the average nitrate concentration is reduced to the desired level.
  • the current density in amps per square centimeter of membrane greatly depends on the ionic strength or resistivity of the tobacco extract, the membranes, the amount of voltage or potential that is being applied, the operating temperature of the stack, the cell thickness, and the resistivity imposed by a certain amount of deposit of tobacco solids on the membranes surface which again depends on viscosity and flow rates.
  • the limiting factors for the desired voltage are the larger capital investment for cells required when the lower voltages are used and the greater transfer of nonionic species across the membranes, the greater probability of membrane "fouling" and the higher power consumption when the higher voltage is applied.
  • Other limiting factors are cell thickness (spacing between membranes), membrane tightness, resistance, ionic strength of the tobacco solubles and membranes and the operating temperature of the system. Voltages of between about 0.5 and 2.0 volts per cell pair permit efficient and economical denitration of tobacco extracts in accordance with the present invention.
  • the pH of the tobacco extract should be kept on the acid side with acids, such as acetic or hydrochloric.
  • acids such as acetic or hydrochloric.
  • water soluble magnesium and calcium salts are maintained in solution, thus preventing the cations from being converted into insoluble hydroxides, carbonates or the like which may deposit on the membrane surface and cause scaling.
  • chemical fouling may be avoided in the treatment of aqueous tobacco extracts by maintaining the pH of the extract below 7.0, normally 5-6.5, with an acid such as acetic.
  • polyvalent cations and anions and peptides may be precipitated and filtered from the extract prior to applying electrodialysis and recombined with the extract thereafter.
  • the most mobile ions such as nitrate
  • the more mobile ions will displace such ions as calcium, magnesium, citrate and the like even from ionic membranes.
  • the electrolyte is in a closed loop recirculating stream in an electrodialysis unit set up such as in FIG. 1, it is continuously gaining metallic ions such as K + , Ca ++ , Mg ++ , and the like. It is thus necessary to continuously adjust the pH with an acid, such as H 2 SO 4 , to prevent any precipitation or scaling of CaSO 4 or Ca(OH) 2 , Mg(OH) 2 or other polyvalent salt. Also, the ionic strength of the electrolyte solution is thus being increased which necessitates a feed and bleed system. It is desirable from a chemistry of smoke standpoint to retain the metallic ions in the denitrated solubles.
  • the electrolyte solution is a system such as potassium acetate and acetic acid, and/or K 2 SO 4 , H 2 SO 4 , it can be recirculated around the electrodes and continuously bled into the exiting denitrated tobacco solubles, thereby eliminating a waste stream and maintaining the potassium level in the denitrated tobacco solubles.
  • the efficiency of the process is enhanced in a system using ion exchange resins and membrane electrodialysis. This is called electro-regenerated ion exchange deionization.
  • the setup is the same as membrane electrodialysis except for the addition of a mixed bed of weak ion exchange or ionic resins to each cell through which the tobacco solubles are to be passed.
  • the dilute solution of ions to be deionized enters the cells that contain the mixed bed of resins.
  • the ions are "trapped" or picked up by the resins causing an increase in ionic concentration and electroconductivity between the electrodes of the electrodialysis cell and thus a lesser amount of electrical power is required.
  • the applied electrical potential causes the anions to transfer through their respective membranes into the brine cells where they are concentrated and removed.
  • the mixed bed of the weak ion exchange resins is continuously regenerated without interruption and without the use of high amounts of additional chemicals or additional power as is the case with standard ion exchangers.
  • the mixed bed of weak ion exchange resins may be composed of a single resin having both negative and positive groups, two different resins, one anionic and one cationic, in bid or "spacer" type form.
  • FIG. 2 is a schematic diagram of the above-described electro-regenerated ion exchange deionization employing a cation permeable membrane, K 2 SO 4 electrolyte solutions and cationic+ and anionic- exchange resins.
  • FIG. 3 depicts the mode of operation in a cell of an electrodialysis stack of the type depicted in FIG. 2.
  • extraction of the tobacco material may be effected with denitrated tobacco extracts.
  • this expedient it is possible to reduce the amount of non-nitrate materials removed from the tobacco since after several extractions the extract liquor will approach saturation. Thus, except for the nitrates, reduced amounts of materials will be removed during subsequent extraction steps. This is a preferred mode of operation for treating tobacco strip or tobacco components intended for use in reconstituted tobacco.
  • the process of the invention may be employed with whole cured tobacco leaf, cut or chopped tobacco, tobacco filler, reconstituted tobacco, tobacco stems and the like.
  • references to tobacco and tobacco materials are to be understood to include all such forms of tobacco.
  • the tobacco treated in accordance with the invention exhibits reduced nitrogen oxide delivery in any tobacco product which is consumed by combustion and that references to smoking tobacco products include cigars, cigarettes, cigarillos, etc.
  • Aqueous tobacco extract containing 46.8% solids and 0.72% NO 3 -N was diluted 1:1 with water and then denitrated with a membrane electrodialysis unit containing 10 cell pairs.
  • the membranes were 9" ⁇ 10" with an effective membrane area of 2.5 ft. 2 .
  • the cells comprised Ionics' 61CZL183 cation permeable paired with 103QZL 183 anion permeable membranes.
  • These anion permeamble membranes are about 0.63 mm thick, contain about 36 weight percent water and comprise crosslinked copolymers of vinyl monomers and contain quarternary ammonium anion exchange groups and are homogeneously film cast in sheet form on a reinforcing synthetic fabric composed of modacrylic polymer.
  • the cation permeable membranes are about 0.6 mm thick, contain about 40 weight percent water and comprise crosslinked sulfonated copolymers of vinyl compounds which are also homogeneously film cast in sheet form on synthetic reinforcing fabrics.
  • the spacers were 0.04".
  • the membranes in front of the electrodes were Ionics' 61AZL-389 which were separated from the platinumniobium, stainless steel electrodes by 0.08" thick spacers.
  • the brine solutions were 0.1% aqueous KNO 3 solutions, and the electrolytes were 0.1 N K 2 SO 4 and H 2 SO 4 having a pH adjusted to 2 to 4.
  • the electrodialysis was effected for the time periods indicated with application of 7.5 volts.
  • the temperature of the solubles during the runs were not controlled and varied between about 88°-98° C.
  • the pH at 22° C. was about 4.75.
  • Table 1 The results are set forth in Table 1.
  • Electrodialysis of tobacco extract was effected in the manner set forth in Example 1, Run 1, with cation permeable CR62SEM and anion permeable AR204UZL Ionics' membranes. These are tighter membranes than those employed in Example 1. Again temperature was not controlled and varied between about 84°-100° C. The results of this run are set forth in Table 2.
  • This brine represents 262.75 g (DWB) of "brine” solids from 1731.2 g (DWB) of tobacco solids of 15.18% “loss” of tobacco soluble solids or 7.6% of tobacco weight since tobacco normally contains 50% soluble solids.
  • Tobacco was pulped with water and the extract containing the solubles was separated and concentrated.
  • the extract was partially denitrated in accordance with the crystallization methods of U.S. Pat. Nos. 4,131,117 and 4,131,118.
  • a portion of the resulting extract was thereupon further denitrated by electrodialysis employing a 20 cell pair unit and the conditions of Example 1 whereby the nitrate was removed as KNO 3 .
  • Half of the resulting denitrated extract was thereupon reapplied to a portion of the tobacco web formed from the extracted pulp and used to form sample cigarettes.
  • a second sample was prepared by adding potassium acetate to the remaining electrodialyzed solubles prior to reapplication to the web.
  • the control sample comprised web treated with the partially denitrated extract.
  • results indicate the effects of denitration on the gas phase smoke constituents. Moreover the results show that restoration of potassium to the denitrated product maximizes the NO reduction and allows additional control of other gas phase constituents in smoke, such as HCN and CO.
  • Tobacco extract was prepared by soaking 20 pounds of bright stems in 50 pounds of water overnight and expressing about 25 pounds of extract from the soaked stems. Two one gallon samples (3800 cc each) of the extract were subjected to electrodialysis employing a 20 cell pair electrodialysis setup, which was otherwise identical to that employed in Example 1. In Run A, 0.75 volts/cell pair was employed whereas in Run B, 1.5 volts/cell pair were employed. The results of these runs are set forth in Table 7.
  • Runs A and B show about 13-16% loss of tobacco solubles for 90% NO 3 -N reduction within 1-2.17 hours.
  • a sample of Run A that had been denitrated by 53.3% was found to have lost only 8.3% of tobacco soluble solids and this 53.3% NO 3 -N reduction was achieved within one hour.
  • Run B 48% NO 3 -N and 6% soluble solids reductions were achieved within 0.33 hour of treatment.
  • the electrodialysis unit was set up using alternating anion permeable and bipolar membranes to form 15 tobacco extract and brine cell pairs in an alternating pattern.
  • the unit also contained an electrolyte cell at each pole.
  • the electrolyte consisted of 0.1 N K 2 SO 4 at a pH of 2-4 (adjusted with H 2 SO 4 ) and contained a small amount of Triton X-100 (non-ionic wetting agent).
  • the bipolar membranes used in the setup were formed by facing one surface of an anion permeable membrane directly in contact with one of the surfaces of a cation permeable membrane resulting in a single bipolar membrane having a positive charge on the surface facing the anode and a negative charge on the surface facing the cathode.
  • the unit was 9" ⁇ 10" with an effective membrane area of 3.75 square feet.
  • the membranes used were Ionics' 103 QZL anion and 61 CZL cation permeable membranes. These membranes were separated by polypropylene spacers 0.04" thick.
  • the membranes in front of the electrodes were Ionics' 61AZL-389 membranes with 0.08" thick polypropylene spacers.
  • a platinum-niobium anode and a strainless cathode were employed.
  • the tobacco solubles passed through the alternating cells that were located on the cathode side of the individual anion permeable membranes. Although the initial pH of the tobacco solubles was approximately 5, during the run the pH tended to become more neutral to basic. Therefore, to maintain the pH between about 5-6 approximately 71.4 grams of glacial acetic acid was used during the run.
  • the brine cells were placed in an alternating pattern on the anode side of the individual anion permeable membranes.
  • the brine solution was 0.1% KNO 3 having an initial pH of 6.
  • the temperature of the various solutions was maintained between 90°-96° F. during the run.
  • the flow rate at 23 psi pumping pressure was set at 1600 cc/minute.
  • an electrical potential of 2 volts/cell pair was applied, the nitrate ions (and chloride ions) were transported from the tobacco solubles towards the anode.
  • the nitrate and chloride ions passed through the anion permeable membranes into the brine cells where they were retained and concentrated.
  • the pH of the brine solution decreased from 6 to 1.
  • a well blended batch of burley tobacco was extracted with hot (90° C.) water using a tobacco/water ratio of 1:25.
  • the wet tobacco was then filtered and pressed under vacuum of 26 psi.
  • the insoluble tobacco residue was allowed to dry at room conditions.
  • the aqueous extract containing the tobacco solubles was concentrated to 15.5% solids and split into two equal portions.
  • the first portion was then selectively dialyzed employing the conditions and electrodialysis setup of Example VI.
  • the second portion was non-selectively electrodialyzed employing a membrane electrodialysis unit as in Example I except 20 cell pairs were employed.
  • Control cigarettes of the same construction and weight as the denitrated cigarettes were formed from untreated tobacco from the same blended batch of burley employed in the extraction of the denitration cigarettes.
  • the data in Table 10 indicates that the denitration of tobacco by electrodialysis reduces such smoke components as NO, HCN and CO.
  • the reductions in NO are practically linear relative to nitrate reduction when the denitration is selective and lesser relative to % NO 3 removed when the denitration is nonselective.

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US06/127,479 1980-03-05 1980-03-05 Method for denitration of tobacco employing electrodialysis Expired - Lifetime US4253929A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US06/127,479 US4253929A (en) 1980-03-05 1980-03-05 Method for denitration of tobacco employing electrodialysis
DE8080105313T DE3069870D1 (en) 1980-03-05 1980-09-05 Method of treating tobacco extracts employing electrodialysis
CA359,584A CA1132943A (en) 1980-03-05 1980-09-05 Method for denitration of tobacco employing electrodialysis
EP80105313A EP0035052B1 (en) 1980-03-05 1980-09-05 Method of treating tobacco extracts employing electrodialysis
US06/216,803 US4302308A (en) 1980-03-05 1980-12-16 Method for electrolytic denitration of tobacco
GR64167A GR73893B (en, 2012) 1980-03-05 1981-02-17
BR8101234A BR8101234A (pt) 1980-03-05 1981-02-27 Processo para desnitracao de extratos aquosos de tabaco e processo para esnitracao de tabaco
JP3109281A JPS56140880A (en) 1980-03-05 1981-03-04 Denitrification of tobacco or extract liquid thereof
DK97481A DK97481A (da) 1980-03-05 1981-03-04 Fremgangsmaade til denitrering af tobak ved hjaelp af elektrodialyse
PH25314A PH16773A (en) 1980-03-05 1981-03-04 Method for denitration of tobacco employing electrodialysis
ES500050A ES8205347A1 (es) 1980-03-05 1981-03-04 Un metodo para eliminar nitrato de extractos de tabaco acuosos por electrodialisis.
AU68080/81A AU540522B2 (en) 1980-03-05 1981-03-04 Denitrification of tobacco by electrodialysis

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EP (1) EP0035052B1 (en, 2012)
JP (1) JPS56140880A (en, 2012)
AU (1) AU540522B2 (en, 2012)
BR (1) BR8101234A (en, 2012)
CA (1) CA1132943A (en, 2012)
DE (1) DE3069870D1 (en, 2012)
DK (1) DK97481A (en, 2012)
ES (1) ES8205347A1 (en, 2012)
GR (1) GR73893B (en, 2012)
PH (1) PH16773A (en, 2012)

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US4364401A (en) * 1980-03-05 1982-12-21 Philip Morris Incorporated Method for selective denitration of tobacco
US4636288A (en) * 1984-01-06 1987-01-13 Vaughan Daniel J Electrodialytic conversion of multivalent metal salts
US4685478A (en) * 1981-10-01 1987-08-11 Philip Morris Incorporated Thermophilic denitrification of tobacco
US4936962A (en) * 1989-03-01 1990-06-26 Fmc Corporation Process for adjusting the pH of an aqueous flowable fluid
US5094732A (en) * 1989-04-28 1992-03-10 Asea Brown Boveri Ltd. Process and apparatus for removing nitrates from a water stream during the treatment of process water
WO1995016806A1 (en) * 1993-12-17 1995-06-22 University Research Foundation Tobacco extract composition and method
US20040202754A1 (en) * 2003-04-11 2004-10-14 Katsunobu Sumimura Method of removing nitrate nitrogen from vegetable juice
US20060065279A1 (en) * 2003-05-06 2006-03-30 Japan Tobacco Inc. Method of manufacturing regenerated tobacco material
US20060162733A1 (en) * 2004-12-01 2006-07-27 Philip Morris Usa Inc. Process of reducing generation of benzo[a]pyrene during smoking
US20080178894A1 (en) * 2007-01-26 2008-07-31 Philip Morris Usa Inc. Methods and apparatus for the selective removal of constituents from aqueous tobacco extracts
CN105029670A (zh) * 2015-08-28 2015-11-11 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Zn含量的选择性降低方法
CN105077560A (zh) * 2015-08-28 2015-11-25 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Se含量的选择性降低方法
CN105124741A (zh) * 2015-08-28 2015-12-09 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Ni含量的选择性降低方法
CN105146721A (zh) * 2015-08-28 2015-12-16 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Pb含量的选择性降低方法
CN105146722A (zh) * 2015-08-28 2015-12-16 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Hg含量的选择性降低方法
CN105169949A (zh) * 2015-08-28 2015-12-23 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中As含量的选择性降低方法
CN106474926A (zh) * 2016-12-26 2017-03-08 合肥科佳高分子材料科技有限公司 一种通过电渗析技术调控烟草提取或萃取液中糖碱比的方法
US10111458B1 (en) 2014-05-16 2018-10-30 R.J. Reynolds Tobacco Company Process for inhibiting formation of nitrosamines
CN108802131A (zh) * 2018-04-28 2018-11-13 深圳市西尔曼科技有限公司 乙酸电极及其制作方法
US10499684B2 (en) * 2016-01-28 2019-12-10 R.J. Reynolds Tobacco Company Tobacco-derived flavorants
CN110693065A (zh) * 2019-09-20 2020-01-17 云南中烟工业有限责任公司 一种在线控制电渗析处理烟梗提取液离子脱除程度的方法
US11091446B2 (en) 2017-03-24 2021-08-17 R.J. Reynolds Tobacco Company Methods of selectively forming substituted pyrazines
CN117378804A (zh) * 2023-11-22 2024-01-12 安徽中烟工业有限责任公司 一种通过置换电渗析系统降低烟草提取液中nh4+离子的方法

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US4301817A (en) * 1980-03-05 1981-11-24 Philip Morris Incorporated Method for selective denitration of tobacco
DE3439900A1 (de) * 1984-10-31 1986-04-30 Alexei 8000 München Filippenko Tabakfeinschnitt
CZ2013234A3 (cs) * 2013-03-28 2014-06-04 Membrain S.R.O. Způsob výroby dusičnanu draselného metodou elektrodialýzy a zařízení k provádění tohoto způsobu
CN104223356A (zh) * 2014-09-03 2014-12-24 云南中烟工业有限责任公司 一种利用两性离子交换膜改善烟草提取物品质的方法
EP4450142A1 (en) * 2021-12-14 2024-10-23 Japan Tobacco Inc. Plant extract production method

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US3645884A (en) * 1969-07-10 1972-02-29 Edwin R Gilliland Electrolytic ion exchange apparatus
US3755135A (en) * 1971-01-20 1973-08-28 A Johnson Electric demineralizing apparatus
US3869376A (en) * 1973-05-14 1975-03-04 Alvaro R Tejeda System for demineralizing water by electrodialysis

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4364401A (en) * 1980-03-05 1982-12-21 Philip Morris Incorporated Method for selective denitration of tobacco
US4685478A (en) * 1981-10-01 1987-08-11 Philip Morris Incorporated Thermophilic denitrification of tobacco
US4636288A (en) * 1984-01-06 1987-01-13 Vaughan Daniel J Electrodialytic conversion of multivalent metal salts
US4936962A (en) * 1989-03-01 1990-06-26 Fmc Corporation Process for adjusting the pH of an aqueous flowable fluid
US5094732A (en) * 1989-04-28 1992-03-10 Asea Brown Boveri Ltd. Process and apparatus for removing nitrates from a water stream during the treatment of process water
US5435941A (en) * 1993-12-17 1995-07-25 University Of Louisville Tobacco extract composition and method
WO1995016806A1 (en) * 1993-12-17 1995-06-22 University Research Foundation Tobacco extract composition and method
US20040202754A1 (en) * 2003-04-11 2004-10-14 Katsunobu Sumimura Method of removing nitrate nitrogen from vegetable juice
US20060065279A1 (en) * 2003-05-06 2006-03-30 Japan Tobacco Inc. Method of manufacturing regenerated tobacco material
RU2310353C2 (ru) * 2003-05-06 2007-11-20 Джапан Тобакко Инк. Способ производства восстановленного табачного материала
US7677253B2 (en) 2003-05-06 2010-03-16 Japan Tobacco Inc. Method of manufacturing regenerated tobacco material
US20060162733A1 (en) * 2004-12-01 2006-07-27 Philip Morris Usa Inc. Process of reducing generation of benzo[a]pyrene during smoking
US20080178894A1 (en) * 2007-01-26 2008-07-31 Philip Morris Usa Inc. Methods and apparatus for the selective removal of constituents from aqueous tobacco extracts
US9049886B2 (en) 2007-01-26 2015-06-09 Philip Morris Usa Inc. Methods and apparatus for the selective removal of constituents from aqueous tobacco extracts
US10111458B1 (en) 2014-05-16 2018-10-30 R.J. Reynolds Tobacco Company Process for inhibiting formation of nitrosamines
CN105029670A (zh) * 2015-08-28 2015-11-11 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Zn含量的选择性降低方法
CN105124741A (zh) * 2015-08-28 2015-12-09 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Ni含量的选择性降低方法
CN105146721A (zh) * 2015-08-28 2015-12-16 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Pb含量的选择性降低方法
CN105146722A (zh) * 2015-08-28 2015-12-16 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Hg含量的选择性降低方法
CN105169949A (zh) * 2015-08-28 2015-12-23 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中As含量的选择性降低方法
CN105077560A (zh) * 2015-08-28 2015-11-25 安徽中烟工业有限责任公司 一种造纸法再造烟叶萃取液中Se含量的选择性降低方法
US10499684B2 (en) * 2016-01-28 2019-12-10 R.J. Reynolds Tobacco Company Tobacco-derived flavorants
CN106474926A (zh) * 2016-12-26 2017-03-08 合肥科佳高分子材料科技有限公司 一种通过电渗析技术调控烟草提取或萃取液中糖碱比的方法
US11091446B2 (en) 2017-03-24 2021-08-17 R.J. Reynolds Tobacco Company Methods of selectively forming substituted pyrazines
US11891364B2 (en) 2017-03-24 2024-02-06 R.J. Reynolds Tobacco Company Methods of selectively forming substituted pyrazines
CN108802131A (zh) * 2018-04-28 2018-11-13 深圳市西尔曼科技有限公司 乙酸电极及其制作方法
CN110693065A (zh) * 2019-09-20 2020-01-17 云南中烟工业有限责任公司 一种在线控制电渗析处理烟梗提取液离子脱除程度的方法
CN117378804A (zh) * 2023-11-22 2024-01-12 安徽中烟工业有限责任公司 一种通过置换电渗析系统降低烟草提取液中nh4+离子的方法

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DE3069870D1 (en) 1985-02-07
BR8101234A (pt) 1981-09-08
CA1132943A (en) 1982-10-05
EP0035052A1 (en) 1981-09-09
JPS56140880A (en) 1981-11-04
GR73893B (en, 2012) 1984-05-16
EP0035052B1 (en) 1984-12-27
ES500050A0 (es) 1982-06-01
ES8205347A1 (es) 1982-06-01
AU6808081A (en) 1981-09-10
AU540522B2 (en) 1984-11-22
JPS5729144B2 (en, 2012) 1982-06-21
DK97481A (da) 1981-09-06
PH16773A (en) 1984-02-22

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